WO2014017805A1 - 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법 - Google Patents

내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법 Download PDF

Info

Publication number
WO2014017805A1
WO2014017805A1 PCT/KR2013/006589 KR2013006589W WO2014017805A1 WO 2014017805 A1 WO2014017805 A1 WO 2014017805A1 KR 2013006589 W KR2013006589 W KR 2013006589W WO 2014017805 A1 WO2014017805 A1 WO 2014017805A1
Authority
WO
WIPO (PCT)
Prior art keywords
zinc alloy
steel sheet
plating
hot
corrosion resistance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2013/006589
Other languages
English (en)
French (fr)
Korean (ko)
Other versions
WO2014017805A8 (ko
Inventor
오민석
진영술
김상헌
김수영
유봉환
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Posco Holdings Inc
Original Assignee
Posco Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Posco Co Ltd filed Critical Posco Co Ltd
Priority to US14/413,530 priority Critical patent/US9745654B2/en
Priority to EP13822651.9A priority patent/EP2876182B1/en
Priority to CN201380039077.3A priority patent/CN104487606A/zh
Priority to ES13822651T priority patent/ES2795986T3/es
Priority to JP2015523019A priority patent/JP6025980B2/ja
Publication of WO2014017805A1 publication Critical patent/WO2014017805A1/ko
Publication of WO2014017805A8 publication Critical patent/WO2014017805A8/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to a hot-dip zinc alloy plated steel sheet widely used in automobiles, home appliances and building materials and the like and a method of manufacturing the same.
  • Zinc plating method that suppresses the corrosion of iron through the cathode method is widely used to produce steel having high corrosion resistance because of excellent corrosion resistance and economic efficiency.
  • hot-dip galvanized steel sheet which forms a plating layer by immersing steel in molten zinc, has a simpler manufacturing process and lower price than electric galvanized steel sheet, and thus is widely used in automobiles, home appliances, and building materials. The demand is increasing.
  • Zinc-plated hot-dip galvanized steel sheet has the characteristic of sacrificial corrosion protection where zinc, which has lower redox potential than iron, is corroded first when steel is exposed to corrosive environment. As the oxide is formed, a dense corrosion product is formed on the surface of the steel sheet to block the steel material from the oxidation atmosphere, thereby improving corrosion resistance of the steel sheet.
  • the temperature of the plating bath should be maintained at 600 ° C or higher.
  • Fe alloy-based dross occurs in the plating bath due to erosion of the base steel sheet, and plating
  • the workability is reduced and the equipment erosion inside the plating bath such as a sink roll is accelerated to shorten the life of the equipment.
  • Zn-Al-Mg alloy plating containing Mg in the Zn-Al-based plating bath has been actively researched for the purpose of reducing the Al content in the plating bath and improving the corrosion resistance of the cut surface and the processed portion. It's going on.
  • Patent Document 1 proposes a method for producing a molten zinc alloy-based plated steel sheet manufactured using a plating bath containing 3 to 17 wt% Al and 1 to 5 wt% Mg.
  • Patent Documents 2 to 4 Plating techniques have been proposed in which corrosion resistance and manufacturing characteristics have been improved by blending various additive elements in a plating bath having the same composition as above or by regulating manufacturing conditions.
  • Mg is lighter and has higher oxidation degree than Zn, which is the main element of the plating composition, so that a large amount of Mg rises to the upper part of the plating bath during the melting process, and the floating Mg is derived from the surface of the plating bath and then oxidized. Cause a large amount of dross. This phenomenon is attached to the steel immersed in the plating bath during the plating process to cause dross defects, thereby making the surface of the plating layer formed on the steel or making the plating operation impossible.
  • Patent Document 5 in manufacturing a Zn-Al-Mg alloy-based plated steel sheet containing 0.06 to 0.25 wt% Al and 0.2 to 3.0 wt% Mg, at least one of Ca, Be and Li is 0.001 to A method of preventing oxidation of the plating bath component and improving workability by adding 0.01 wt% has been proposed.
  • the addition amount of the added element is very small, so it is not easy to test the efficacy of the added element, and the Al content is very low at 0.25 wt% or less, so that only the alloy composition in which the amount of Mg oxidizing dross is formed in the plating bath is large. It is targeted.
  • Patent Document 6 discloses 0.01 to 1.0 wt% Ti and 0.01 to 2.0 in producing a Zn-Al-Mg alloy-based plated steel sheet containing 1 to 4 wt% Al and 2 to 20 wt% Mg.
  • a method of suppressing dross generation by adding wt% Na has been proposed.
  • the melting temperature of Ti is 1668 ° C, which is too high compared to the plating bath temperature
  • the specific gravity of Na is 0.96g / cm 3 , which is too low compared to the Zn specific gravity of 7.13g / cm 3 , so that these elements are actually added to the plating bath. There is a problem that is not easy to do.
  • a trace element may be added for the purpose of improving the corrosion resistance of the plating material.
  • Patent Document 7 in addition to a plating bath containing 2 to 19 wt% Al, 1 to 10 wt% Mg, and 0.01 to 2.0 wt% Si, 0.01 to 1.0 wt% In and 0.01 to 1.0 wt% Bi And 1-10 wt% of Sn or more to propose a method of improving the corrosion resistance of the formed plating layer.
  • the inventors have studied this, and when Si is added to the plating bath containing Al and Mg, much more dross of the plating bath occurs than the plating bath without the addition of Si, resulting in surface defects of the plating layer. It was confirmed to cause.
  • the Mg 2 Si phase and Zn-Al-Mg-Si four-way interfacial alloy phase that is inevitably formed inside the plating layer due to the addition of Si increases the hardness of the plating layer, and increases the crack width of the processed portion formed during processing. It has been confirmed that this results in worse corrosion resistance.
  • Patent Document 1 US Patent No. 3,505,043
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2000-104154
  • Patent Document 3 Japanese Laid-Open Patent No. 1999-140615
  • Patent Document 4 International Publication No. WO06 / 002843
  • Patent Document 5 Japanese Patent Application Laid-Open No. 1996-060324
  • Patent Document 6 Korean Laid-Open Patent No. 2002-0041029
  • Patent Document 7 Korean Laid-Open Patent No. 2002-0019446
  • An aspect of the present invention is to provide a hot-dip zinc alloy plated steel sheet excellent in corrosion resistance and surface appearance produced using a Zn-Al-Mg-based hot-dip zinc alloy plating bath and a method of manufacturing the same.
  • One aspect of the present invention includes a base steel sheet and a hot-dip zinc alloy plating layer, the composition of the hot-dip zinc alloy plating layer in weight%, aluminum (Al): 0.5 ⁇ 5.0%, magnesium (Mg): 1 ⁇ 5% Contains one or two of gallium (Ga): 0.01% to 0.1% and indium (In): 0.005% to 0.1%, and includes residual zinc (Zn) and unavoidable impurities. Provides a hot-dip zinc alloy plated steel sheet having excellent corrosion resistance and surface appearance, which satisfies the relationship of [Al + Mg ⁇ 7].
  • the present invention by improving the plating workability by adding a small amount of Mg antioxidant element to effectively suppress the occurrence of dross formed on the plating bath by the oxidation reaction of Mg added to improve the corrosion resistance of the galvanized layer.
  • Mg antioxidant element to effectively suppress the occurrence of dross formed on the plating bath by the oxidation reaction of Mg added to improve the corrosion resistance of the galvanized layer.
  • Figure 1 shows the observation of the plating structure in the plating layer of the hot-dip zinc alloy plated steel sheet according to the present invention.
  • Figure 2 shows the observation of the plating structure of the plating layer according to the cooling rate.
  • Figure 3 shows the result of measuring the weight of the dross generated on the bath surface of the plating bath according to the composition of the molten zinc alloy plating bath.
  • Figure 4 shows the results of the salt spray test of the plated steel sheet subjected to the plating process by using the respective hot dip zinc alloy plating bath having different composition components.
  • the molten zinc alloy plating bath used in the present invention is a weight percent, aluminum (Al): 0.5 to 5.0%, magnesium (Mg): 1 to 5%, gallium (Ga): 0.01 to 0.1% and indium ( In): It comprises one or two of 0.005 to 0.1%, and it contains the balance zinc (Zn) and unavoidable impurities, it is preferable that the component ratio of Mg and Al satisfies the relationship of [Al + Mg ⁇ 7] .
  • Mg of the components in the hot-dip zinc alloy plating bath plays a very important role in improving the corrosion resistance of the plating layer, and Mg contained in the plating layer shows the growth of a zinc oxide-based corrosion product having a small effect of improving the corrosion resistance in a severe corrosion environment. Suppresses, stabilizes the corrosion resistance of the zinc hydroxide-based corrosion-producing products with a high effect of improving corrosion resistance on the surface of the plating layer.
  • the Mg component content is less than 1% by weight, the effect of improving the corrosion resistance by Zn-Mg-based compound formation is not sufficient.
  • the content of Mg is more than 5% by weight, the effect of improving corrosion resistance is saturated, and the Mg oxidizing dross is There is a problem that surges in the bathing surface of the plating bath. Therefore, in the present invention, it is preferable to control the Mg content in the plating bath to 1 to 5% by weight.
  • Al is added for the purpose of reducing the dross caused by the Mg oxidation reaction in the Mg addition zinc alloy plating bath, Al is also combined with Zn and Mg to improve the corrosion resistance of the plated steel sheet do.
  • the Al content is less than 0.5% by weight, the effect of preventing oxidation of the plating bath surface layer by Mg addition is insufficient, and the effect of improving corrosion resistance is small.
  • the Al content exceeds 5.0% by weight, the amount of Fe eluted from the steel plate immersed in the plating bath is increased so that Fe alloy dross is formed, and the weldability of the plating layer is further deteriorated. Therefore, in the present invention, it is preferable to control the Al content in the plating bath to 0.5 to 5.0% by weight.
  • Ga or In is added in one kind or two kinds, in order to reduce the formation of the upper surface dross of the bath surface by preventing Mg oxidation of the bath surface. .
  • the Ga or In also serves to improve the corrosion resistance of the plated steel sheet by reducing the amount of Fe elution of the steel sheet immersed in the plating bath to reduce the production of Fe alloy dross.
  • the Ga content is preferably 0.01 to 0.1 wt%, and the In content is 0.005 to 0.1 wt%.
  • the respective content exceeds 0.1% by weight, grain boundary segregation may be induced and the corrosion resistance of the plating layer may be lowered. Therefore, each content is limited to 0.1% by weight or less.
  • the plating layer is added by adding a small amount of Ga or In, which is more effective in preventing Mg oxidation.
  • the plating bath dross resulting from Mg oxidation can be reduced, but the Fe elution of a steel plate can be suppressed, without maintaining the Al content of the high.
  • these elements do not change other physical properties other than improving the corrosion resistance of the plating layer, and do not significantly change the conventional use of the plating bath.
  • the plating bath upper dross formation was suppressed and the plating workability was improved.
  • Al and Mg are both elements for improving the corrosion resistance of the plating layer, and as the sum of these elements increases, the corrosion resistance may be improved. However, when the sum of Al and Mg weight percent in the plating bath exceeds 7.0%, the effect of improving the corrosion resistance is saturated, while the hardness of the plating layer is increased to promote work cracking, deterioration of weldability and paintability. Or a need for improvement of the treatment method.
  • the hot-dip zinc alloy plated steel sheet of the present invention comprises a base steel sheet and a hot-dip zinc alloy plated layer, the composition of the hot-dip zinc alloy plated layer by weight, Al: 0.5 to 5.0%, Mg: 1 to 5%, Ga : 0.01 to 0.1% and In: 0.005 to 0.1% of one or two, containing the balance Zn and unavoidable impurities, the component ratio of the Mg and Al satisfies the relationship of [Al + Mg ⁇ 7] It is preferable.
  • the hot-dip zinc alloy plated layer formed by the above-described composition is preferably attached at a plating amount of 10 to 500 g / m 2 based on one side. If the plating amount is less than 10g / m 2 based on one side, it is difficult to expect anti-corrosive properties, while the one-side plating amount is more than 500g / m 2 disadvantageous economically.
  • plating in order to achieve the alloy plating to have high corrosion resistance, it is preferable to perform plating with a plating amount in the range of 10 to 500 g / m 2 .
  • coated tissue is also in the molten zinc alloy plating layer, and a Zn-Al-MgZn 2 3 won process organized in matrix organization, Zn-MgZn 2 2 won process organization and includes a dispersion-coated tissue , Al and Zn single phase tissues are uniformly distributed crystal structure, the rest includes MgZn 2 tissue.
  • the single phase in the plating layer Formation of the tissue is affected by the cooling rate in the future cooling step (see Figure 2).
  • the roughness of the roll during the temper rolling becomes difficult to be uniformly transferred to the steel sheet, and thus there is a problem that the surface roughness after the temper rolling is unevenly formed.
  • the rougher the surface of the plating layer the easier the roughness of the roll during temper rolling is uniformly transferred to the steel sheet. Therefore, it is preferable to lower the roughness of the plating layer before temper rolling as much as possible. Therefore, in the present invention, it is preferable to manage the surface roughness Ra of the hot-dip zinc alloy plated steel sheet to 1 ⁇ m or less.
  • Method for producing a hot-dip zinc alloy plated steel sheet of the present invention comprises the steps of preparing the hot-dip zinc alloy plating bath; Immersing a base steel sheet in the molten zinc alloy plating bath and performing plating to manufacture a plated steel sheet; And gas wiping the plated steel sheet.
  • the plating bath temperature at the time of ordinary hot-dip zinc alloy plating can be applied, and the plating is preferably performed in the plating bath in the range of 380 to 450 ° C. can do.
  • the temperature of the plating bath should be increased.
  • the base steel sheet and the plating bath internal equipment are eroded, which may shorten the life of the equipment and increase the Fe alloy dross in the plating bath, thereby deteriorating the surface of the plating material.
  • the Al content is controlled to be relatively low at 0.5 to 5.0% by weight, it is not necessary to set the temperature of the plating bath high, and it is preferable to apply a conventional plating bath temperature.
  • the coating amount may be adjusted by gas wiping the steel plate on which the plating layer is formed.
  • the gas wiping is for adjusting the plating deposition amount, and the method is not particularly limited.
  • air or nitrogen may be used as the gas used, and more preferably, nitrogen is used. This is because Mg oxidation occurs preferentially on the surface of the plating layer when air is used, which may cause surface defects of the plating layer.
  • cooling may be performed.
  • cooling it is preferable to cool rapidly at a cooling rate of 10 ° C / s or more, and preferably to the end of the solidification immediately after the gas wiping.
  • the plating structure of the plated layer is changed according to the cooling rate. If the cooling rate is slower than 10 ° C./s, the Zn single phase increases, and the increased Zn single phase adversely affects the corrosion resistance of the steel sheet. Referring to FIG. 2, it can be seen that when the cooling rate is less than 10 ° C./s, the formation of Zn single phase in the plating structure is increased, compared to the case where the cooling rate is 10 ° C./s or more.
  • cooling when cooling at the above cooling rate, a conventional cooling method capable of cooling the plating layer may be used.
  • cooling may be performed by using an air jet cooler or spraying N 2 wiping or water fog. .
  • the plating bath After completely removing the dross caused by other impurities contained in the ingot itself in the drying bath of the plating bath, the plating bath was exposed to an atmosphere in which the plating bath could be oxidized while maintaining the temperature of the plating bath at 440 ° C. After the plating bath was maintained for 24 hours under the above conditions, the dross formed on the bath surface of the plating bath was collected, and the weight thereof was measured.
  • a low carbon cold rolled steel sheet having a thickness of 0.8 mm, a width of 100 mm, and a length of 200 mm was prepared as a steel sheet, and the ultrasonic steel plate was immersed in acetone and ultrasonically cleaned on the surface. Foreign substances, such as the rolling oil which existed, were removed.
  • the plating test piece was heat-treated in a 750 ° C. reducing atmosphere and cooled to 470 ° C. before being introduced into the plating bath.
  • the composition of the plating bath was prepared as shown in Table 2 below, the temperature of the plating bath was maintained at 450 °C.
  • the cooled test piece was immersed in each plating bath of Table 2 for 3 seconds, and then the plating adhesion was adjusted by N 2 gas wiping to prepare a plated steel sheet.
  • the plated steel sheets having a single-sided plating amount of 60 g / m 2 were selected and evaluated for physical properties such as surface appearance, dross reduction effect, and corrosion resistance of these coated steel sheets, and the results are shown in Table 2 and FIG. 4.
  • X Surface roughness exceeding 3 micrometers, a plating layer is nonuniform and a large amount of plating defects generate
  • Dross Reduction Effect During the plating process, the surface of the plating bath is left in the air for 1 hour, and then the dross generated on the surface of the plating bath is visually observed.
  • Corrosion resistance After the corrosion promotion test is carried out by the salt spray test (salt spray standard test according to KS-C-0223), measure the time elapsed until the red blue color area of the plating layer reaches 5%.
  • the cold-rolled steel sheet was heat-treated in a 750 °C reducing atmosphere before manufacturing the plated steel sheet, the dew point inside the Snout (Snout) during the plating process was maintained at -40 °C.
  • the composition of the plating bath was prepared as shown in Table 3 below, the temperature of the plating bath was maintained at 440 °C.
  • the cold rolled steel sheet was immersed in each plating bath of Table 3 for 3 seconds, and after the plating was completed, the steel sheet was cooled at a rate of 10 ° C / s.
  • Dross weight After 100m continuous plating of cold rolled steel plate without surface scale, the weight of dross generated on the bath surface of the plating bath is measured.
  • Fe content in dross After plating, a certain amount of dross is taken from each plating bath, chip processed, dissolved in dilute hydrochloric acid solution, and the solution is analyzed by ICP (Inductively Coupled Plasma).
  • the inhibition of dross formation of the bath surface of the plating bath is due to the reduction of Fe content of the dross due to the oxidation prevention of Mg mentioned above and the addition of a small amount of Ga or In. It is believed that this is because Fe inhibits elution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Thermal Sciences (AREA)
  • Coating With Molten Metal (AREA)
PCT/KR2013/006589 2012-07-23 2013-07-23 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법 Ceased WO2014017805A1 (ko)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US14/413,530 US9745654B2 (en) 2012-07-23 2013-07-23 Hot dip zinc alloy plated steel sheet having excellent corrosion resistance and external surface and method for manufacturing same
EP13822651.9A EP2876182B1 (en) 2012-07-23 2013-07-23 Hot dip zinc alloy plated steel sheet having excellent corrosion resistance and external surface and method for manufacturing same
CN201380039077.3A CN104487606A (zh) 2012-07-23 2013-07-23 具有优异的耐腐蚀性和外表面的热浸锌合金镀覆钢板及其制造方法
ES13822651T ES2795986T3 (es) 2012-07-23 2013-07-23 Chapa de acero revestida con aleación de zinc por inmersión en caliente que tiene excelente resistencia a la corrosión y superficie externa y procedimiento para fabricar la misma
JP2015523019A JP6025980B2 (ja) 2012-07-23 2013-07-23 耐食性及び表面外観に優れた溶融亜鉛合金めっき鋼板及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020120080021A KR101417304B1 (ko) 2012-07-23 2012-07-23 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법
KR10-2012-0080021 2012-07-23

Publications (2)

Publication Number Publication Date
WO2014017805A1 true WO2014017805A1 (ko) 2014-01-30
WO2014017805A8 WO2014017805A8 (ko) 2014-12-11

Family

ID=49997554

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/006589 Ceased WO2014017805A1 (ko) 2012-07-23 2013-07-23 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법

Country Status (7)

Country Link
US (1) US9745654B2 (enExample)
EP (1) EP2876182B1 (enExample)
JP (1) JP6025980B2 (enExample)
KR (1) KR101417304B1 (enExample)
CN (1) CN104487606A (enExample)
ES (1) ES2795986T3 (enExample)
WO (1) WO2014017805A1 (enExample)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015001368A1 (fr) * 2013-07-04 2015-01-08 Arcelormittal Investigaciòn Y Desarrollo Sl Procédé de traitement d'une tôle pour réduire son noircissement ou son ternissement lors de son stockage et tôle traitée par un tel procédé
KR101746955B1 (ko) * 2015-10-26 2017-06-14 주식회사 포스코 내스크래치성이 우수한 도금 강선 및 그 제조방법
JP6983153B2 (ja) * 2015-10-26 2021-12-17 ポスコPosco 曲げ加工性に優れた亜鉛合金めっき鋼板及びその製造方法
CN105483590B (zh) * 2015-12-20 2018-06-15 安徽伟宏钢结构集团股份有限公司 一种钢构件热浸镀锌工艺
KR102075182B1 (ko) 2015-12-24 2020-02-10 주식회사 포스코 도금성이 우수한 고강도 용융 아연계 도금 강재 및 그 제조방법
KR101847567B1 (ko) * 2015-12-24 2018-04-10 주식회사 포스코 미세하고 균일한 도금 조직을 갖는 도금 강판
CN105671469B (zh) * 2016-03-22 2018-08-21 首钢集团有限公司 一种热浸镀钢及其制造方法
EP3497258B1 (en) * 2016-08-08 2024-02-21 Colorado School of Mines Modified hot-dip galvanize coatings with low liquidus temperature, methods of making and using the same
KR101858862B1 (ko) * 2016-12-22 2018-05-17 주식회사 포스코 크랙 저항성이 우수한 합금도금강재 및 그 제조방법
SG11201906851UA (en) * 2017-01-27 2019-08-27 Nippon Steel Corp Metalic coated steel product
KR102031466B1 (ko) 2017-12-26 2019-10-11 주식회사 포스코 표면품질 및 내식성이 우수한 아연합금도금강재 및 그 제조방법
KR102142766B1 (ko) 2018-08-31 2020-08-07 주식회사 포스코 내식성 및 가공성이 우수한 용융도금강판 및 이의 제조방법
DE102020208991A1 (de) * 2020-07-17 2022-01-20 Thyssenkrupp Steel Europe Ag Verfahren zur Herstellung eines schmelztauchbeschichteten Stahlblechs und schmelztauchbeschichtetes Stahlblech
CA3195998A1 (en) * 2020-11-18 2022-05-27 Kotaro Ishii Plated steel material
KR102453011B1 (ko) 2020-12-21 2022-10-12 주식회사 포스코 실러 접착성이 우수한 도금 강판 및 이의 제조방법
CN116837253A (zh) * 2022-06-21 2023-10-03 湘潭大学 一种能有效抑制硅反应性且耐蚀性优良的镀锌合金
CN116752067B (zh) * 2023-07-26 2025-09-23 株洲冶炼集团股份有限公司 一种锌浴控铁热镀用锌合金

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505043A (en) 1969-01-08 1970-04-07 Inland Steel Co Al-mg-zn alloy coated ferrous metal sheet
JPH0860324A (ja) 1994-08-22 1996-03-05 Kawasaki Steel Corp 耐食性に優れたＺｎ−Ｍｇ−Ａｌ系溶融めっき鋼材およびその製造方法
JPH10226865A (ja) * 1996-12-13 1998-08-25 Nisshin Steel Co Ltd 耐食性および表面外観の良好な溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造法
JPH11140615A (ja) 1997-11-04 1999-05-25 Nisshin Steel Co Ltd Ｍｇ含有溶融Ｚｎ基めっき鋼板
JP2000104154A (ja) 1998-07-02 2000-04-11 Nippon Steel Corp 耐食性に優れためっき鋼板と塗装鋼板及びその製造方法
KR20020019446A (ko) 1999-05-24 2002-03-12 아사무라 타카싯 내식성이 우수한 도금 강재, 도금 강판과 도장 강판 및 그제조방법
KR20020041029A (ko) 2000-11-25 2002-06-01 이구택 내식성이 우수한 용융아연합금계 도금강판
JP2002206156A (ja) * 2000-11-06 2002-07-26 Nippon Steel Corp 鉄塔用めっき鉄鋼製品とその製造方法および該製造方法で用いるフラックス
JP2002285311A (ja) * 2001-03-23 2002-10-03 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造方法
JP2003138359A (ja) * 2001-10-29 2003-05-14 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇ−Ｚｒ合金めっき鋼板およびその製造方法
KR20050068257A (ko) * 2003-12-29 2005-07-05 주식회사 포스코 표면외관이 미려한 용융아연도금강판의 제조방법
WO2006002843A1 (en) 2004-06-29 2006-01-12 Corus Staal Bv Steel sheet with hot dip galvanized zinc alloy coating and process to produce it

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69730212T2 (de) * 1996-12-13 2005-08-18 Nisshin Steel Co., Ltd. HEISSTAUCH Zn-Al-Mg BESCHICHTETES STAHLBLECH MIT HERVORRAGENDEN KORROSIONSEIGENSCHAFTEN UND OBERFLÄCHENAUSSEHEN UND VERFAHREN ZUR HERSTELLUNG
JP4968701B2 (ja) * 2000-08-28 2012-07-04 新日本製鐵株式会社 外観の良好な溶融Ｚｎめっき高強度鋼材
JP3779941B2 (ja) * 2002-01-09 2006-05-31 新日本製鐵株式会社 塗装後耐食性と塗装鮮映性に優れた亜鉛めっき鋼板
JP2003328101A (ja) 2002-05-16 2003-11-19 Nippon Steel Corp 溶融めっき鋼線およびその製造方法
JP2004019000A (ja) 2002-06-20 2004-01-22 Sumitomo Metal Ind Ltd 外観、加工性、耐食性に優れた溶融Ｚｎ−Ａｌめっき鋼板とその製造方法
JP4374281B2 (ja) * 2004-05-26 2009-12-02 新日本製鐵株式会社 加工部耐食性に優れる溶融めっき鋼材
RU2470088C2 (ru) * 2010-10-29 2012-12-20 Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) Расплав на основе цинка для нанесения защитных покрытий на стальную полосу горячим погружением

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505043A (en) 1969-01-08 1970-04-07 Inland Steel Co Al-mg-zn alloy coated ferrous metal sheet
JPH0860324A (ja) 1994-08-22 1996-03-05 Kawasaki Steel Corp 耐食性に優れたＺｎ−Ｍｇ−Ａｌ系溶融めっき鋼材およびその製造方法
JPH10226865A (ja) * 1996-12-13 1998-08-25 Nisshin Steel Co Ltd 耐食性および表面外観の良好な溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造法
JPH11140615A (ja) 1997-11-04 1999-05-25 Nisshin Steel Co Ltd Ｍｇ含有溶融Ｚｎ基めっき鋼板
JP2000104154A (ja) 1998-07-02 2000-04-11 Nippon Steel Corp 耐食性に優れためっき鋼板と塗装鋼板及びその製造方法
KR20020019446A (ko) 1999-05-24 2002-03-12 아사무라 타카싯 내식성이 우수한 도금 강재, 도금 강판과 도장 강판 및 그제조방법
JP2002206156A (ja) * 2000-11-06 2002-07-26 Nippon Steel Corp 鉄塔用めっき鉄鋼製品とその製造方法および該製造方法で用いるフラックス
KR20020041029A (ko) 2000-11-25 2002-06-01 이구택 내식성이 우수한 용융아연합금계 도금강판
JP2002285311A (ja) * 2001-03-23 2002-10-03 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造方法
JP2003138359A (ja) * 2001-10-29 2003-05-14 Sumitomo Metal Ind Ltd 溶融Ｚｎ−Ａｌ−Ｍｇ−Ｚｒ合金めっき鋼板およびその製造方法
KR20050068257A (ko) * 2003-12-29 2005-07-05 주식회사 포스코 표면외관이 미려한 용융아연도금강판의 제조방법
WO2006002843A1 (en) 2004-06-29 2006-01-12 Corus Staal Bv Steel sheet with hot dip galvanized zinc alloy coating and process to produce it

Also Published As

Publication number Publication date
US9745654B2 (en) 2017-08-29
EP2876182A4 (en) 2016-04-27
EP2876182B1 (en) 2020-03-11
JP2015531817A (ja) 2015-11-05
EP2876182A1 (en) 2015-05-27
WO2014017805A8 (ko) 2014-12-11
KR101417304B1 (ko) 2014-07-08
CN104487606A (zh) 2015-04-01
JP6025980B2 (ja) 2016-11-16
ES2795986T3 (es) 2020-11-25
US20150159253A1 (en) 2015-06-11
KR20140013334A (ko) 2014-02-05

Similar Documents

Publication Publication Date Title
WO2014017805A1 (ko) 내식성 및 표면외관이 우수한 용융아연합금 도금강판 및 그 제조방법
WO2012091385A2 (en) High corrosion resistant hot dip zn alloy plated steel sheet and method of manufacturing the same
WO2019132337A1 (ko) 표면품질 및 내식성이 우수한 아연합금도금강재 및 그 제조방법
WO2021060879A1 (ko) 내식성, 내골링성, 가공성 및 표면 품질이 우수한 도금 강판 및 이의 제조방법
WO2021125630A1 (ko) 가공부 내식성이 우수한 Zn-Al-Mg계 용융합금도금 강재 및 그 제조방법
WO2019132336A1 (ko) 가공 후 내식성 우수한 아연합금도금강재 및 그 제조방법
WO2015099455A1 (ko) 액체금속취화에 의한 크랙 저항성이 우수한 용융아연도금강판
WO2019132461A1 (ko) 열간 프레스 성형용 도금강판, 이를 이용한 성형부재 및 이들의 제조방법
WO2018117714A1 (ko) 용접성 및 프레스 가공성이 우수한 용융 아연계 도금강재 및 그 제조방법
WO2018124649A1 (ko) 점용접성 및 내식성이 우수한 다층 아연합금도금강재
WO2021112519A1 (ko) 굽힘 가공성 및 내식성이 우수한 용융아연도금강판 및 이의 제조방법
WO2018038499A1 (ko) 내골링성, 성형성 및 실러 접착성이 우수한 용융 아연도금 강판 및 그 제조방법
WO2022124825A1 (ko) 도금품질이 우수한 고강도 용융아연도금강판, 도금용 강판 및 이들의 제조방법
KR20120076111A (ko) 우수한 내식성, 가공성 및 외관을 제공하는 용융아연도금욕 및 그에 의해 도금된 강판
WO2020111775A1 (ko) 도금 밀착성 및 내부식성이 우수한 아연도금강판 및 이의 제조방법
WO2022124826A1 (ko) 도금품질이 우수한 고강도 용융아연도금강판, 도금용 강판 및 이들의 제조방법
WO2016105163A1 (ko) 용접성 및 가공부 내식성이 우수한 아연합금도금강재 및 그 제조방법
WO2019132412A1 (ko) 내식성 및 표면 평활성이 우수한 아연합금도금강재 및 그 제조방법
WO2013100610A1 (ko) 고망간 열연 아연도금강판 및 그 제조방법
WO2017026683A1 (ko) 표면외관이 우수한 전기아연도금강판용 아연 플래쉬 도금 용액, 이를 이용한 전기아연도금강판의 제조방법 및 전기아연도금강판
WO2016093667A1 (ko) 도금 조성물, 이를 이용한 도금 강재의 제조방법 및 도금 조성물이 코팅된 도금 강재
WO2023055073A1 (ko) 내식성 및 백색도가 우수한 도금 강판 및 이의 제조방법
WO2018117703A1 (ko) 희생방식성 및 도금성이 우수한 고망간 용융 알루미늄 도금강판 및 그 제조방법
WO2018117770A1 (ko) 가공부 내식성이 우수한 알루미늄계 합금 도금강판
WO2016105157A1 (ko) 인산염 처리성과 스폿 용접성이 우수한 아연합금도금강판 및 그 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13822651

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 14413530

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2015523019

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2013822651

Country of ref document: EP